A textile material coated with an ammonium dialkyl phosphate antistatic agent

ABSTRACT

Acyl-amino-propyl-dialkyl-ammonium dialkyl phosphates as surface active agents and their application to textile materials, especially polyester and polyamide fibrous materials, as a finishing agent, for example, in combination with an aqueous emulsion of a textile lubricating agent.

United States Patent 1 1 3,634,! 17

[72] Inventors Arno Wegerhoff [50] Field of Search 1 17/1395 Worth, am Main; F, 139.5 0, 138.8 F,138.8 N; 252/88, 8.9 Franz-Josef Schmitz, Erlenbach; Carl Macura, Klingenberg, all of Germany [56] References cued [21 Appl. No. 799,999 UNITED STATES PATENTS 12 1 Filed Feb 17,1969 2,233,001 2 1941 Dickey 117/1395 [45] Patented Jan. 11, 1972 2,676,122 4/1954 McCarthy 117/139.5 Assignee GlanzsmffAG 2,742,379 4/1956 McGrew 117/1395 x W pp r a m ny 2,853,451 9/1958 Fortess et al. 117/139.5 X [32] Priority Feb. 17, 1968 3,364,142 1/1968 Buck 252/8.8 1 Germany 3,493,504 2/1970 Buckley 117 139.5 x [31] P17 19543.6

Primary ExammerW1ll1am D. Martin Assistant Examiner-Theodore G. Davis [54] TEXTILE MATERIAL COATED WITH AN Attorney-Johnston, Root, OKeeffe, Keil, Thompson &

AMMONIUM DlALKYL PHOSPHATE ANTISTATIC Shurfleff AGENT 7 Claims No Drawings ABSTRACT: Acyl-amino-propyl-dialkyl-ammonium dialkyl [52] [1.5. CI ..117/l38.8F, phosphates as Surface acti e agents and their application to l 7/l3 N, 252/88, 252/89, 1 17/1 9 Q textile materials, especially polyester and polyamide fibrous [51] lnt.Cl ..D06m 13/26 i l as a finishing agent, for example, in combination with an aqueous emulsion ofa textile lubricating agent.

A TEXTILE MATERIAL COATED WITH AN AMMONIUM DIALKYL PHOSPHATE ANTISTATIC AGENT The use of amine salts of polyethoxyalkyl phosphoric acid esters of the formula as antielectrostatic finishing agents for polyethylene terephthalate filaments and fibers has been described in German Patent specification No. 1,084,231. The amine portion of this phosphoric acid ester salt consists of a monoamine, e.g., an alkyl amine or an alkylol amine. Diethanolamine salts of mixtures of alkyl esters of pentavalent phosphorus acids or acid anhydrides, characterized by the presence of PO P- linkages, are described in U.S. Pat. No. 2,742,379 as having antistatic properties in their application to hydrophobic textile materials.

N-substituted diamines can form the cation of the quaternary ammonium salts ll of the formula:

which also have antistatic properties (see U.S. Pat. No.,

3,082,227). In these salts of the formula ll, the radical R is an aliphatic or alicyclic hydrocarbon of at least seven carbon atoms, two of the primed Rs maybe a lower alkyl but at least one is a monohydroxyalkyl of two or three carbon atoms, and Y is the anion of an inorganic acid.

There are literally thousands of organic compounds in addition to those mentioned above which possess antistatic properties and which have therefore been suggested for application to hydrophobic synthetic polymer products, especially textile materials, in order to reduce the electrostatic charging of these products as they are being processed and/or during subsequent use. It is extremely difficult, however, to find suitable antistatic agents which are fully compatible with other finishing agents such as lubricants, sizes, emulsifiers and the like. Moreover, many antistatic agents possess other proper ties which make them relatively unsatisfactory in such applications e.g., where the antistatic agent contributes to the corrosion of machinery used in processing the treated textile materials or where it is not stable or resistant to subsequent heat treatment steps. These and similar problems as well as the desirability of improving the antistatic effect must be taken into consideration in attempting to provide satisfactory finishing agents of this type.

One object of the present invention is to provide a class of organic compounds which are highly useful in a finishing or lubricating composition for textile materials, and to provide a process for treating such textile materials to achieve an improved antistatic effect.

Another object of the invention is to provide an antistatic agent which can also function as an emulsifying agent for textile lubricants and which possesses a number of desirable properties for this use or similar applications.

Still other objects and advantages of the invention are explained in greater detail hereinafter.

It has now been found, in accordance with the invention, that especially improved results can be achieved in terms of antistatic effect with a finishing agent and compositions containing the same by means of a phosphate of the formula Ill, especially when applied as a preparatory and finishing agent for fibrous or filamentary polyester and polyamide textile materials; in which formula R represents a primary n-alkyl group of five to l7 carbon atoms, i.e., an alkyl group offrom C H to C H R, and R each represent a lower alkyl radical of one to three carbon atoms;

R represents a lower alkyl radical of two to four carbon atoms; and

R represents an alkyl radical of two to 18 carbon atoms, preferably a primary n-alkyl group.

Of particular technical and commercial significance are the phosphoric acid ester amine salts which may be identified as l-lauramidopropyl-dimethylammonium-( 3 )-ethyl primary-nalkyl phosphates which have the structural formula:

in which R is alkyl and preferably the primary n-alkyl group ofabout two to 18 and preferably four to 14 carbon atoms.

Depending on the length of the alkyl chains in the cation and anion, respectively, the amine salts used in accordance with the invention are either cationically active or anionically v active, or may be both cationically and anionically active.

The effectiveness of these compounds is not limited to the improved electrostatic properties imparted to polyester and polyamide yarns, filaments or fibers and to textiles containing these materials, but also extends to other filaments and fibers so as to greatly facilitate their mechanical handling during drawing or carding operations or in knitting and weaving machinery. The amino phosphoric acid ester salts of the formulas ill or IV, when used according to the invention, thus reduce the static and sliding friction ofa wide variety of natural and synthetic fibers and also that of metal or rubber, so as to be generally useful as an antistatic agent. The finishing or antistatic agents of the invention are also extremely resistant to heat. For example, during the heat fixing or setting of synthetic thermoplastic filaments, the phosphate compounds of the invention do not cause any yellowing of the fibrous material finished with these compounds. Also, these finishing agents do not cause any alteration in the electrical and mechanical properties of the filaments during heat treatment.

The emulsifying properties of the phosphate compounds permit, inter alia, the preparation of stable emulsions of When applied to unalloyed steel components, e.g., by vaporization of a 1 percent aqueous solution on a steel plate, the amine salts according to the invention actually prevent rust formation. Thus, the dialkyl phosphates listed in table 1 below have a notable corrosion-inhibiting action. By comparison, the quaternary ammonium salts ll according to U.S. Pat. No. 3,082,227 are not too satisfactory in this respect, and in fact, the salts of strong inorganic acids as disclosed in this patent actually promote the formation of rust.

The antielectrostatic effect is particularly pronounced with the l-lauramidopropyl-dimethylammonium-( 3 )-ethyl primary-n-alkyl phosphates of the structural formula lV, especially when these amine salts form a thin surface layer on polyesters, e.g., polyethylene terephthalate, or on polyamide (nylon) yarns, filaments or fibers, including fabrics or other textile products. Those salts having R of two up to six carbon atoms, e.g., the primary nC,,H,,-, group, are fully soluble in water. With larger alkyl radicals R e.g., up to 18 carbon atoms, they can still be dispersed in water, so that the impregnation of any materials to be treated is best accomplished in an aqueous solution or dispersion.

Strips of a polycaprolactam fabric, which have been treated under controlled conditions with aqueous solutions of these phosphates, then dried and rubbed over stainless steel pins, show a distinctly lower electrostatic charging than a comparison strip of polycaprolactam fabric which has a surface film or coating of the sodium slat of the copolymer of styrene and maleic acid which is a well known antistatic agent (see example 1 below).

With medium length alkyl radicals R e.g., six to eight carbon atoms, the lauramidopropyl-dimethylammonium-dialkyl phosphates IV are soluble both in water and hydrocarbon solvents, e.g., turpentines or so-called white spirit as well as mineral oils in general, and exhibit especially good emulsifying properties because of their boundary surface activity. For example, when the ethyl primary-n-hexylphosphate V is combined with an ethoxylated oleyl alcohol VI which contains about two ethylene oxide groups per alcohol molecule, an emulsifier system is formed which permits mineral oils or similar lubricants to be emulsified in water. An optimum emulsifying action has been produced when parts by weight of the ethoxylated oleyl alcohol V] are used to 13 parts by weight of the amine salt V. With a ratio by weight of this emulsifier system to mineral oil of 23:30, a 10 percent by weight emulsion of the mineral oil in water is transparent. With increasing mineral oil content, the aqueous emulsions assume a milky cloudiness because of particle enlargement. In a comparison sample using only the ethoxylated oleyl alcohol, mineral oil and water, and in which no ammonium phosphate such as compound V is present, it is not possible to obtain a stable emulsion.

Aqueous emulsions of these components are particularly suitable for use as finishing and lubricating compositions in the processing of synthetic yarns, filaments or fibers, since they lower the friction and protect steel contact surfaces from rust formation, as well as decreasing the electrostatic charging. In addition to the use of the ammonium dialkyl phosphates Ill alone, mixtures of these compounds with other emulsifiers are also feasible. In particular, mixtures of V and VI have been found especially useful as dressings for the processing of polyester staple fibers. The addition of the ethoxylated oleyl alcohol VI to the amine phosphate salt V increases the slippability as compared to fibers dressed only with the salt V. With a composition consisting of equal parts by weight of V and VI, addition of about 0.1 percent by weight to a dried 3-denier polyethylene terephthalate fibrous material is sufficient in order to almost completely eliminate electrostatic charging during carding. By comparison, when using a commercial product which is an ethoxylated stearic acid ester, the electrostatic charging is substantially higher even after application of four times as much of the active agent (see example 3 below).

Mixtures of one part by weight of the dialkylphosphate V to about one to two parts by weight of the ethoxylated oleyl alcohol Vl also provide good finishing agents for those polyester or polyamide fibers which are processed on cards or by the converted method. Such finishing compositions reduce the static and sliding friction of the fibers both relative to one another and also to metal or rubber. This makes its possible to process these fibers satisfactorily, for example, on a Rieter converter, followed by machines which are customary in the spinning of combed yarn.

Mixtures of phosphoric acid ester amine salts of the structural formula IV and ethoxylated oleyl alcohol Vl do not cause any yellowing of polyethylene terephthalate fibers or other thermoplastic fibers after these have been set or heat treated for one hour at [50 C. Furthermore, the electrical and mechanical properties of such fibers or filaments are not modified by this heat treatment.

A comparison of the salts III of the acylated dimethylamino-3-propylamine and dialkyl phosphoric acids according to salts described in US. Pat. No. 2,742,379 shows the decided superiority of the salts Ill over the known diethanolamine salts of the cited patent, particularly as finishing agents with an antielectrostatic effect. Thus, the Hanramidopropyl-dimethylammonium-(3)-ethyl primary-n-alkyl phosphates lV, at relatively low atmospheric humidities, have a better antielectrostatic action on fabrics consisting of polyamide or polyester fibers than the compounds according to U.S. Pat. No. 2,742,379. Also, the antielectrostatic efiect of the amine salts Ill used according to the present invention on woven fabrics, e.g., consisting of polyester fibers, has been proven to be more heat resistant than that of the prior art compounds.

The tertiary amines with an acid amide group, which are required as the intermediate product for the preparation of the acylated tertiary ammonium dialkyl phosphates Ill, can be produced in accordance with the following procedure, generally by reacting higher fatty acids with dimethylaminopropylamine:

3.8 kg. (19 mols) of lauric acid and 2.54 kg. (25 mols) of dimethylamino-propylamine are heated for 1 hour at 145 C. and the mixture is boiled gently. Within another 4 hours, the temperature is slowly raised to 200 C. The excess amine is then distilled off, together with the water produced in the reaction. The last residues of the dimethylamino-propylamine can also be removed under vacuum, the pressure being slowly reduced within an hour to 13 to 15 mm. Hg. The residue of llauramidopropyl-3dimethylamide, which is similar to a grain or curd soap, melts at 33.5to 35.5 C.

The dialkyl phosphoric acids used for neutralizing this amine intermediate are obtained by methods generally well known and similar to that given in German Patent specification No. 1,084,231 for the production of polyethoxy ethyl phosphoric acids. For neutralization purposes, i.e., to produce the amine salt [I], equimolar quantities of amine and dialkyl phosphoric acid are stirred together at 50 to 60 C. for about 15 minutes.

The invention is further illustrated but not limited by the following examples. All parts and percentages are by weight unless otherwise indicated.

EXAMPLE I Strips measuring 5X85 cm. of a polycaprolactam woven fabric are dipped at room temperature into various baths of an 0.5 percent aqueous solution of a number of the different I- lauramido-propyl-dimethylammonium-(3)-ethyl primary-nalkyl phosphates IV (see table I). The amine salts which are used differ only in the length of the alkyl radical R in the phosphate anion. The fabric strips are then wrung out until they contain about percent moisture, dried for 20 hours in air and rubbed on stainless steel pins. The rubbing movement can be effected using a suitable mechanical device, always under the same mechanical conditions. With an atmosphere of 44 percent relative humidity at 23 C., the maximum charges listed in table 1 are measured with a Feldmuhle instrument, with a spacing being provided between the fabric and the measuring head ofthe instrument of 30 mm.

In addition to the maximum charges, table 1 also gives the charges prior to the rubbing operation, designated as precharge, and the discharge times. In those cases where the electrostatic charge was low, the discharge was generally so quick that the field decay could not be accurately controlled with the measuring arrangement being used. Such a rapid field decay is given in all of the tables 1, 2, 4, 5, and 6 below as a time reading of l second, i.e., less than I second. With a slower field decay which can be clearly measured, the discharge times are set forth as being measured from the termination of the rubbing movement, at which time it has reached the maximum charge, until there has been a discharge to +0.5 or 0.5 kv./m. or to the indicated value.

The determination of the applied amounts of the antistatic agent is effected by weighing the untreated and impregnated fabric strips, and the amount is set forth as percentage by weight with reference to the dry fabric. The Copolymer A is the sodium salt of the copolymer of styrene and maleic acid which is a readily available commercial product normally used as an antistatic agent for polyamides, and which is used for a comparison of the antielectrostatic effects. The discharge of the strips of polycaprolactam fabric, finished with the ammonium dialkyl phosphates IV, takes place substantially more quickly than with the substrate treated with the sodium salt of the copolymer.

TABLE 1 Maximum charging and discharge capacity of strips of polycaprolactam fabric, impregnated with the salts IV of lauramidopropyl-dimethylamine-(3) and ethyl primary-nalkyl phosphoric acids, and with Copolymer A (the sodium salt of the copolymer of styrene and maleic acid) as a comparison substance:

finishing agent: C H A R G 1 N G lnstead of strips of polycaprolactam fabric as used in example l, fabric strips of polyethylene terephthalate fibers were examined in the same way as in example 1. The results are given in table 2. Serving as a comparison product was the stearamidopropyl-dimethyl-B-hydroxyethylammonium-(3)- phosphate Vll, which is known and is also obtainable commercially as an antistatic agent.

As will be seen from table 2, the fabric strips treated with the dialkyl phosphates IV become chargedto a substantially smaller degree than those finished with the comparison substance. There is no difference with regards to the speed of the discharge.

TABLE 2 Maximum charging and discharging capacity of fabric strips of polyethylene terephthalate fibers, impregnated with the salts IV of l-lauramidopropyl-dimethylamine-(3) and ethyl primary-n-alkyl phosphoric acids, and the quaternary ammonium phosphate Vll as a comparison substance, respectively:

A mixture which proved suitable for use as a dressing or finishing agent for polyethylene terephthalate fibers is a mixture of equal parts by weight of l-lauramidopropyldimethylammonium-(3)-ethyl primary-n-hexyl phosphate V and an oleyl alcohol which has been etherified with 2 mols ethylene oxide Vl. Polyethylene terephthalate fibers (3.0 denier; staple length 60 mm.) are dressed for 30 seconds at 70 C. in aqueous solutions containing dissolved therein the mixture defined above. The bath ratio is 1:20, and the bath concentrations which are used are given in table 3. After centrifuging to about 7 percent absorption of the bath solution, the fibers are dried for 15 minutes at C. with air circulation and conditioned for 24 hours in an atmosphere of air maintained at 54 to 58 percent relative humidity and a temperature of 22 to 24 C. A commercially available finishing agent for polyester fibers, based on an ethoxylated stearic acid ester is used as the comparison substance. The finished fibrous flocks are carded and the electrostatic charges on the resulting nonwoven fiber fleece are measured with a Feldmuhle instrument under the same conditions. The results are given in table 3, together with the bath concentrations and the electrical resistivities measured on the fibrous flocks at 65 percent relative humidity and 20 C. With the exception of the comparison sample, the capacity of the fibers for carding is quite suitable in all three cases. It is known that electrostatic charges below about 10,000 v./m. represent a limiting value for this purpose. With the comparison example, a bath concentration of more than 6 percent had to be used in order to produce an adequate antielectrostatic effect. However, the larger application of such a textile auxiliary has been found from experience to impair the working properties of the fibers because the static friction on metal and rubber is too great.

TABLE 3 Electrical resistivities of finished polyethylene terephthalate fibrous flocks and electrostatic charges, measured during carding of the nonwoven fibrous fleece material:

Comparison tests were made in these examples with the antielectrostatic finishing agents according to the invention and U.S. Pat. No. 2,742,379.

The phosphoric acid ester amine salts 111 according to the invention were prepared as set forth herein, and the comparison products were obtained according to U.S. Pat. No. 2,742,379.

An examination of the antistatic effects of the preparations under different air humidity conditions was carried out.

For the investigation of the antistatic effects, fabric strips of polyethylene terephthalate fibers (example 4) and polycaprolactum fibers (example 5) were impregnated by the method described in example 1 with the l-lauramidopropyl-diemthylammonium-(3)-ethyl primary-n-alkyl phosphates 1V and, after drying in air, they were conditioned for 24 hours in air:

at 20 C. and 30 percent relative humidity, and

at 20 C. and 65 percent relative humidity.

The radical R in the cation of the dialkylphosphate IV was selected as n-hexyl-(l), n-octyl-(l) and n-decyl-( l respectively, in order to test three different compounds of the invention.

The electrostatic charge was produced, always under the same mechanical conditions, by rubbing on stainless steel pins, and the same procedure was used for estimating the antistatic efficiency as in examples 1 and 2. This charge was measured with a Feldmuhle measuring instrument under the atmospheric conditions indicated, the distance between the fabric and measuring head being 30 mm.

The substances described in examples I, ii and III of US. Pat. No. 2,742,379 (hereinafter referredto as Comparison Products I, ii, and Ill) were also tested in the same way for fabrics finished with the amine salts lV acquire a decidedly lower electrostatic charge than the fabric strips treated with the comparison products I, ii, and ill. As shown in tables 4 and 5, the improvement in the antistatic effectiveness thus their antistatic effectiveness. The results are given in tables 4 5 d d i bli hed f l h l ne t hth l f b i and together with the amounts PP The determination and also for polycaprolactam fabrics. At 20 C. and 30 percent of the amounts applied was accomplished by weighing the unrelative humidity, the effect is more apparent than at 20 C. tre and the impr gn and dried fabric P In addiand 65 percent relative humidity. Whereas the amine salts IV, tion to the maximum charges produced by rubbing, table 4 at 20 C. and 30 percent relative humidity, were more effecand table 5 also give the so-called precharges, to. the ele r tive antistatically on both polyethylene terephthalate fabrics static Charges f re he ru g operat on. as Well as the and polycaprolactam fabrics than the Comparison Products i i h rg im example to II], this difference could only be established in the case of polycaprolactam fabric at 20 C. and 65 percent relative hu- TABLE 4 midity. As already mentioned, the comparison of the charging Maximum charging and discharge capacity f f b i Strips values listed in tables 4 and 5 were made, taking into account of polyethylene terephthalate, impregnated with the salts IV the PP quanmle5- of l-lauramidopropyl-dimethylamine-(3) and ethyl primary-n- EXAMPLE 6 alkyl phosphoric acids, and with the Comparison Products I, T t f h h t t bT f th ff f h I], and II], respectively. Discharge time with all specimens 1 es s e ea 5 a l o e am'sta 6 em 0 t 6 Second preparations were made.

in order to check the heat stability of the antistatic effect of Atmw the preparations, strips of polyethylene terephthalate fabric hel'lc Eleetfowere impregnated with the amine salts IV and with the Comcon tions static Finishing agent; Amount (1/ Maximum par1s0n Products I, ii, and III, as described in the previous exfifgge gi g g gg 9 1:353 pfi fg g Egg/8 1 i g amples 4 and 5, and after being dried at room temperature, p were treated for 45 minutes with hot air at 140 C. The change gg Qgg 188% g in the antistatic effect was tested by measuring the charges by -Tl-CmH2 0. 31 20/30 +0103 0. 1 the method described in example i, and after 24 hours condiconipanso pmduct: 0.32 20/30 +0.04 tioning in air at 20 C. and 30 percent relative air humidity.

0. 24 20/30 +0. 02 -14 before and after the hot air treatment. 20/30 +0'02 Before the hot air treatment, the maximum electrostatic 41-8.?" 0. 46 20/66 +0.02 +0.02 charges, both with the amine salts IV and with the Comparison :ficf fig' 812% 18:85 $8 8; Products i, ll, and ill, with values in the region of +50 v./m., 0 32 20/65 02 0 02 were approximately equal to the precharging, so that charging 20/65 1 1 differences could not be established, because of the relatively Q24 20/65 good antistatic effect of both types of finishing agents. This 0.45 20/30 3 1 does not contradict the results of table 4, since the measureg-gg :g-& ment values listed in table 4 were established using fabric 7 strips with applications of 0.2 to 0.8 percent, while the deter- 8; $2 28538 i8: 8 4% mination of the hot air stability on fabric strips took place with 0.58 20/30 +0.03 0.3 applications of about 1 percent and more. After the hot air 0. 20/65 01 01 treatment, the values given in table 6 were obtained. 0. 64 20/65 0. 01 O. 01 5 0. 20/65 02 025 TABLE 6 0.83 20/65 5:0 *0 Maximum charge and discharging capacity of fabric strips 8-82 33%? 32 9% of polyethylene terephthalate, impregnated with amine salts IV of l-lauramidopropyl-dimethylamine-(3) and ethyl prima- 5O ry-n-alky] phosphoric acids and with the Comparison Products TABLE 5 I, ii, and ill, respectively, after hot air treatment for 45 minutes at C., atmospheric conditions: 20 Cl/30 percent Maximum charging and discharge capacity of fabric strips relafive humidity. of polycaprolactam, impregnated with the salts IV of l-lauramido-propyl-dimethylamine-(3) and ethyl primary-n-alkyi It can be seen from the values of table 6 that the antistatic phosphoric acids, and with the Comparison Products I, ii and efficiency of the Comparison Products I, ii and III is conlll, respectively: siderably lessened after hot air treatment whereas the anti- Atmospheric Discharge Amount conditions Electrostatic Maximum time to- Finishin agent: Amine salt applied, O./percent Prechargin charge =l=0.5 kv./rn. IV with 4 as listed below. percent rel. hum.) (kv./m. (kv./m.) (sec.)

-n-C5Hr; 0. 51 20/30 +0. 04 1. 3 1 -n-C3H 7 0. 81 20/30 +0. 04 -O. 2 -n-C1oHz| 0. 68 20/30 +0. 04 2 Comparison product:

0. 51 20/65 +0. 02 0. 81 20/65 +0. 02 -n-C1oH:i 0. 68 20/65 +0. 02 Comparison product:

The comparison of the electrostatic effectiveness of the' amine salts IV with the comparison Products I, ii and ill shows that, when taking into account the applied quantities, the

static effect is only slightly reduced in the case of the amine salts lV. It must also be appreciated that, as already stated, approximately the same good antistatic effect exists before the Elem) Dischamo ethoxilated lauryl alcohol which contains about five ethylene static pretime to oxide groups er alcohol molecule, and l .p.m. l-lau- Finishing agent: Amount charging Maximum 0. d pylmegh l i (3 gh l.. .dg Amine salts with R4 applied, max. charge kv./ni. as listed below percent (kv./m.) (kv./m.) (500.) Phosphate formula ii 2a- I R2 Ih .1= 2 0 91 +0 1 H R ,nC H The mixture is heated under stirring to 1: 23 +0: 1 5060 C. By this manner a clear oil is received. The emulsion is made by adding under stirring l to ppm. of this oil to 80 1' 66 1 ppm. water at room temperature. 1 18% The invention is hereby claimed as follows:

1. A fibrous textile material selected from the class consisting of fibrous polyesters and polyamides coated with a small antistatic effective amount of a phosphate of the formula hot air treatment.

In carrying out numerous tests in accordance with the preceding examples, it has been found that one can generally G9 employ the finishing agent of the invention, i.e., compounds 15 R-C-NI{--CII C1I;CII NII O=P-O-R4 III, in an aqueous bath having a concentration of the finishing R2 agent of about 0.5 to 10 percent by weight. The amount of this 0 finishing agent applied to textile fibers, i.e., as filaments, wherein, yarns, fabrics or the like, should ordinarily be about 0.05 to l R represents a p y malkyl g p of five to 7 carbon percent by weight, taken with reference to the dry fibers (after 20 atoms. evaporation of the water). R and each r t lk 1 Other finishing or emulsifying agents, such as the ethoxy- 2 repress a y of one to three carbon lated oleyl alcohol may also be added to the bath, e.g., in a concentration ofabout l to 5 percent by weight. R1 represents alkyl oftwo to 18 carbon atoms- A Suitable lubricating agent Such as the known mineral Oils 2. A fibrous textile material as claimed in claim 1 wherein may generally be added to the aqueous finishing composition Said phosphate has the formula in amounts of about 1 to 15 percent by weight, with reference R represents alkyl of two to four carbon atoms; and

to the water. Since these lubricating agents are usually water a; 0 AH5 insoluble and relatively instable when emulsified in water, the CnHz,-;CNHCH1CHzCHz-NH OPORi compositions of the present invention are especially valuable CH3 in providing highly stable emulsions which even remain clear with up to about 10 percent by weight ofa mineral oil emulsified in water. In addition to their emulsifying properties, the in which K is a primary n-alkyl group of two to 18 carbon finishing agents of the invention also have good corrosion-inatoms.

hibiting properties so as to be especially useful as a preparato- 3. A fibrous textile material as claimed in claim 1 wherein ry or dressing agent where the textile filaments, yarns, threads, said phosphate has the formula etc., are conducted through many textile operations in contact 0 CH3 O C2H5 with steel machinery. The capacity of the textile material to be H worked mechanically is also improved CiiH2a-CNHCHzCHzCH2NII O=P-(llCsH|3) In all of the examples herein, the primary-n-alkyl groups are CH,

generally designated simply as n-alkyl with the empirical formula for the particular alkyl group, e.g. primary-n-hexyl" I Y is given as urkcfiplwn These Straight Chain alkyl radicals are 4. A fibrous textile material as claimed in claim 1 wherein generally preferred for purposes of the present invention, the amount of said phosphate coated on said textile material is either as the radical R or as the radical R in the structural forabout l Percem by welght, with Tefefeme I0 h dry mulas III and iv. fibers- Although the working examples above are directed to the 5. A fibrous textile material coated with about 0.05 to l per- Compounds IV as especially preferred finishing agents, good Gem by we'ght thereofofa Phosphate ofthe formula results in terms of antistatic effect, emulsifying properties I? M and/or heat stability have also been established with other 5 CH CH compounds falling within the scope ofthe structural formula: 2 2 2 e i R 0 R1 OR; 2 0 ll 83 l R-C-NH-CHCH2CH2-NH O=PO R4 wherein:

R represents a primary n-alky group of five to 17 carbon n- III alkyl TABLE 7 Maximum charging and discharge capacity of fabric strips of polycaprolactam Compound III Amount Maximum Discharge applied, charge time to 0.5

Ex. No. R R1 R2 R3 R4 percent (kv./m.) kv./m. (sec.)

5 l1 CH3 CH3 C2H6 n-CmHzi 0. 31 0. 2 -CrHu CH3 CH3 CzHs n-CmHu 0. 33 l. 7 1 h-CmHzi CH3 CH3 C2H5 n-CwI-Iz 0. 38 0. 3 n-CnHss CH3 CH3 C2H5 It-CmHz 0. 35 0. 2 llH23 CH3 CH3 n-CiHu Il-CmHzi 0. 40 +0. 03 Copolymer A (comparison) 0.33 2. 0 15 11-0511 CH3 CH3 CzHs ll-C1oHz| O. 76 +0. 03 iHis CH3 CH3 CzHs n-CwHn 0. 73 +0. 03 I1CIJH27 CH3 CH3 CzHs Il-CmHz O. 81 +0. 03 nHaa CH3 CH3 C2H5 ll-CmHzi 0. 75 +0. 03 n-CuHza CH3 CH3 n-C4Hn n-C Hn 0.72 +0. 02 Copolymer A (comparison) 0. 71 l. 6

R and R each represent alkyl of one to three carbon EXAMPLE awn;

R represents alkyl of two to four carbon atoms; and

A stable aqueous emulsion is prepared as follows: To 3 to 6 75 R represents alk l f t t 18 carbon ato P-P- mineral Oil (Viscosity: P- 31 C, boiling 6. The product of claim 5 wherein said fibrous textile range: 2700-3350 at o are added 2 P-P- of an material is composed ofa hydrophobic synthetic polymer.

3 5 lOlOIR (MAR 7. The product of claim 5 wherein said fibrous textile material is also coated with a mineral oil lubricating agent.

UNITED STA "ES PATENT OFFECE CEB'HFICATE OF COERECTECY Patent 165M111? Dated Januarv 11. 19:72

Inventor(s) Arno wegerhoff, Franz-Josef Schmitz, and Carl Macura It is certified that: error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 1, delete "A" Column 2, line 18, that portion of the formula reading "R" shoul read R Column 3, line 6, "slat" should read salt line 57, "converted" should read converter Column line .216, "lauramidopropyl-3-dimethylamide" should read lauramldopropyl-5-dimethylamine Column 5, Table II, opposite -n-C H "-0. 06" should. read -O. 14 line 75, "2 mols" should read 2 mole of Column 6, line 59, lactum" should read lactam line 60, "diemthyl' should read dimethyl Column 10, line 4, should read R line 28, that portion of the formula reading "A H should read C H lines 57 to 41, ona I [CuHzr kN]I-CH:CI12CIHNII should read I: fr 6; /cm Cul[z.xC-NII-CIIaCHzCIIy-NII L Signed and sealed this 31st day of October 1972.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents 

2. A fibrous textile material as claimed in claim 1 wherein said phosphate has the formula in which R4 is a primary n-alkyl group of two to 18 carbon atoms.
 3. A fibrous textile material as claimed in claim 1 wherein said phosphate has the formula
 4. A fibrous textile material as claimed in claim 1 wherein the amount of said phosphate coated on said textile material is about 0.05 to 1 percent by weight, with reference to the dry fibers.
 5. A fibrous textile material coated with about 0.05 to 1 percent by weight thereof of a phosphate of the formula wherein: R represents a primary n-alky group of five to 17 carbon n-alkyl R1 and R2 each represent alkyl of one to three carbon atoms; R3 represents alkyl of two to four carbon atoms; and R4 represents alkyl of two to 18 carbon atoms.
 6. The product of claim 5 wherein said fibrous textile material is composed of a hydrophobic synthetic polymer.
 7. The product of claim 5 wherein said fibrous textile material is also coated with a mineral oil lubricating agent. 